Zinc-Mediated Transmetalation as a Route to Anionic N-Heterocyclic Olefin Complexes in the p-Block

Anionic N-heterocyclic olefins (aNHOs) are suited well for the stabilization of low-coordinate inorganic complexes, due to their steric tunability and strong sigma- and pi-electron donating abilities. In this study, the new two-coordinate zinc complex ((Me)eIPFCH)(2)Zn ((IPrCH)-I-Me = [(MeCNDipp)(2)C=CH](-), Dipp = 2,6-diisopropylphenyl) is shown to participate in a broad range of metathesis reactions with main group element-based halides and hydrides. In the case of the group 14 halides, Cl2E.dioxane (E = Ge and Sn), transmetalation occurs to form dinuclear propellane-shaped cations, [((IPICHE)-I-Me)(2)(mu-Cl](+), while the aNHO-capped phosphine ligand (IPrCH)-I-Me-PPh2 is obtained when ((Me)lPrCH)(2)Zn is combined with CIPPh2. Lastly, ZnH2 elimination drives transmetalation between ((Me)lPrCH)(2) Zn and hydroboranes and hydroalumanes, leading to Lewis acidic aNHO-supported -boryl and -alane products.